CN110919019A - Preparation method of high-purity ruthenium powder - Google Patents
Preparation method of high-purity ruthenium powder Download PDFInfo
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- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 77
- 239000000843 powder Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 230000009467 reduction Effects 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000001257 hydrogen Substances 0.000 claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 18
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000004821 distillation Methods 0.000 claims abstract description 14
- 238000001556 precipitation Methods 0.000 claims abstract description 11
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims abstract description 11
- 230000001590 oxidative effect Effects 0.000 claims abstract description 10
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical class [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 239000000460 chlorine Substances 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 14
- 238000010521 absorption reaction Methods 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 229910001927 ruthenium tetroxide Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 6
- 239000012498 ultrapure water Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- -1 polytetrafluoroethylene Polymers 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 235000009161 Espostoa lanata Nutrition 0.000 claims description 3
- 240000001624 Espostoa lanata Species 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 abstract description 12
- 239000002245 particle Substances 0.000 abstract description 10
- 239000012535 impurity Substances 0.000 abstract description 8
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 abstract description 6
- 235000019270 ammonium chloride Nutrition 0.000 abstract description 5
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 238000004663 powder metallurgy Methods 0.000 abstract description 2
- 239000013077 target material Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001036 glow-discharge mass spectrometry Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000005477 sputtering target Methods 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910001361 White metal Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 210000000795 conjunctiva Anatomy 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- JGJLWPGRMCADHB-UHFFFAOYSA-N hypobromite Inorganic materials Br[O-] JGJLWPGRMCADHB-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- XUXNAKZDHHEHPC-UHFFFAOYSA-M sodium bromate Chemical compound [Na+].[O-]Br(=O)=O XUXNAKZDHHEHPC-UHFFFAOYSA-M 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000002061 vacuum sublimation Methods 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010969 white metal Substances 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
- B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
- B22F9/26—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions using gaseous reductors
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention relates to the technical field of powder metallurgy, in particular to a preparation method of high-purity ruthenium powder. Aims to solve the problems of low product purity and large impurity amount in the prior art. The invention comprises the following steps: (1) introducing chlorine gas for oxidation under an alkaline condition, and carrying out oxidative distillation: (2) NH4Cl precipitation to obtain (NH4)2RuCl6 precipitation; (3) carrying out high-pressure hydrothermal reduction to obtain pure ruthenium and ruthenium oxide; (4) hydrogen thermal reduction is carried out to obtain the high-purity micron-level ruthenium powder product. Has the advantages that: the process flow is simple and easy to implement, the purity of the ruthenium powder is more than 99.999%, the free-running property is good, and the particle size is 2-20 mu m.
Description
Technical Field
The invention relates to the technical field of powder metallurgy, in particular to a preparation method of high-purity ruthenium powder.
Background
Ruthenium is a hard white metal with a density of 12.30g/cm, a melting point of 2310 ℃ and a boiling point of 3900 ℃, the oxidation state of ruthenium is +1, +2, +3, +4, +5, +6, +7 and +8, ruthenium has a strong tendency to form coordination compounds, such as K4[ Ru (CN)6] ∙ 3H2O, K3[ RuCl6] Na2[ RuCl4O2], and the oxide RuO4 of ruthenium is a highly toxic volatile compound and has strong stimulation on the conjunctiva and respiratory tract of human eyes. Ruthenium is chemically stable, and has resistance to common acids including aqua regia and hydrofluoric acid and phosphoric acid at 100 deg.C, and iodine in chlorine water, bromine water and alcohol can slightly corrode ruthenium at room temperature. Resistance to many molten metals including lead, lithium, potassium, sodium, copper, silver and gold. With molten alkaline hydroxides, carbonates and cyanides. The high-purity Ru powder can be used as the intermediate layer material of magnetic recording medium, and can be widely used in computer hard disk and semiconductor memory integrated circuit. The high-purity ruthenium powder is mainly used for preparing ruthenium target materials, and the ruthenium target has strict requirements on purity and morphology structure. The line width process of 0.35 μm has a chemical purity of more than 99.995%, the line width process of 0.25 μm has a chemical purity of more than 99.999%, even more than 99.9999%, the content of impurities such as alkali metals, transition metal elements, radioactive elements, gas elements and the like is required to be very low, the granularity is required to be controlled below 100 μm, and in order to improve the compactness, equiaxial grains such as spheres are optimal, and the more regular and uniform the morphology of ruthenium powder is, the more favorable the preparation of the target material is. A ruthenium oxide film is formed by sputtering a ruthenium target in an oxygen atmosphere as a low electrode material of a metal oxide semiconductor capacitor. Currently known production methods include a chemical precipitation-hydrogen reduction method, an electron beam melting method, a ruthenium dioxide hydrogen reduction method, and the like. However, the ruthenium powder prepared by the methods has low purity, irregular appearance, uneven particle size distribution, poor powder fluidity and low tap density. Therefore, it is very important to develop a new way for preparing ruthenium powder.
In the comparison document, patent document 1, publication No. CN103223493A, discloses a process for preparing high purity ruthenium powder: adding crude ruthenium powder into NaOH solution, reacting to generate RuO4 to volatilize under the oxidation action of chlorine, absorbing by hydrochloric acid, heating and concentrating the absorbing solution to be viscous, adding NaBrO3 into the concentrated solution under the acidic condition, absorbing the volatilized RuO4 by hydrochloric acid, concentrating again, and repeating for three times; concentrating the ruthenium absorption liquid to 30-60g/L, adding an oxidant to convert Ru (III) into Ru (IV), heating to 80 ℃, adding excessive NH4Cl to precipitate ruthenium in the form of (NH4)2RuCl6, filtering, washing, drying, calcining, reducing hydrogen to obtain aggregated ruthenium particles, and performing high-energy ball milling to obtain ruthenium powder with the purity of 99.99% and the morphology structure meeting the requirement of sputtering target materials. The method has the problem of introducing new impurities in the ball milling process.
In the comparison, patent document 2, publication No. CN106392058A, discloses a method for preparing ruthenium powder. The process is as follows: based on the difference between the boiling point and the vapor pressure of ruthenium and other impurity elements, the vacuum sublimation technology is applied to carry out physical sublimation purification on the 99.9 percent coarse ruthenium powder, and main metal impurities such as Fe, Ca, Cu, Mg, Ni, K, Cr, Na and the like are volatilized in the process, so that the high-purity ruthenium powder with the purity of more than 99.995 percent can be prepared. The method does not mention the morphology of ruthenium powder.
In a reference, patent document 3, publication No. US6458183, discloses a method for preparing ruthenium powder. The specific process is that ozone is introduced into a fluidized bed containing coarse ruthenium powder, the coarse ruthenium powder is oxidized into ruthenium tetroxide gas which enters another reactor along with redundant ozone, the ruthenium tetroxide is decomposed into ruthenium dioxide in the reactor, and the ruthenium dioxide in the reactor is introduced with hydrogen for reduction to obtain ruthenium powder with the purity of 99.99 percent. The purity of the ruthenium powder prepared by the method is not enough, and the purity of the ruthenium powder for the sputtering target material cannot be met.
In conclusion, the ruthenium powder product in the prior art has the problems of low product purity and large impurity amount.
Disclosure of Invention
The invention aims to solve the problems of low product purity and large impurity amount in the prior art.
The specific scheme of the invention is as follows:
a preparation method of high-purity micron-sized ruthenium powder is designed, and comprises the following steps:
(1) oxidative distillation: putting 99.9% of coarse ruthenium powder into a three-neck bottle, introducing chlorine gas to oxidize under alkaline condition, and oxidizing a product RuO4Absorbing by using a seven-grade hydrochloric acid absorption liquid to obtain a chlororuthenic acid solution;
（2）.NH4cl precipitation: placing the chlorine ruthenic acid solution obtained in the step (1) into a double-layer glass reaction kettle for stirring and heating, and adding superior pure NH under the stirring condition4Cl, cooling to room temperature and filtering to obtain (NH)4)2RuCl6Precipitating;
(3) high pressure hydrothermal reduction: reacting (NH) obtained in step (2)4)2RuCl6Adding ultrapure water into the precipitate, stirring and slurrying to obtain suspension, and adding the suspension into a polytetrafluoroethylene liningIntroducing hydrogen into the autoclave for reduction under the condition of high-pressure hydrothermal reduction to obtain pure ruthenium and ruthenium oxide;
(4) thermal reduction in hydrogen: and (4) putting the ruthenium and the ruthenium oxide obtained in the step (3) into a tubular furnace, and introducing hydrogen for reduction to obtain a high-purity micron-grade ruthenium powder product.
The alkaline condition is that a saturated NaOH solution is added into a three-mouth bottle, the mass ratio of the coarse ruthenium powder to the NaOH is 1: 2-1: 5, and the ratio of the absorption liquid hydrochloric acid to the ultrapure water is 1: 1.
In step (1), the progress and end point of distillation were checked by using a cotton ball dipped in wet acidic thiourea in an absorption tube.
NH described in step (2)4The conditions for Cl precipitation were: the concentration of the chlororuthenic acid solution is controlled to be 10-50 g/L, and the temperature is controlled to be 50-100 ℃.
The high-pressure hydrothermal reduction conditions in the step (3) are as follows: the reduction temperature is 80-120 ℃, and the reduction time is 2-5 h.
And (4) carrying out hydrogen thermal reduction on ruthenium and ruthenium oxide at the drying temperature of 100 ℃, drying for 24 hours, wherein the reduction temperature is 500-900 ℃, and the reduction time is 1-5 hours.
The invention has the beneficial effects that:
the high-purity micron-sized ruthenium powder is prepared by the processes of oxidative distillation, high-pressure hydrothermal reduction and the like, the process flow is simple, the implementation is easy, the purity of the obtained powder is more than 99.999%, the particle size is micron-sized, the free-running property is good, the particle size is 2-20 microns, and the polyethylene lining can ensure the purity of the product in the processing process.
Drawings
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is an XRD analysis pattern of ruthenium powder according to the present invention;
FIG. 3 is an SEM image of ruthenium powder according to the present invention.
Detailed Description
The preferred embodiments of the present invention will be described in conjunction with the accompanying drawings, and it will be understood that they are described herein for the purpose of illustration and explanation and not limitation.
Example 1
A method 9 for preparing high-purity micron-sized ruthenium powder, which is shown in fig. 1 to 3, and comprises the following steps:
(1) oxidative distillation: putting 99.9% of coarse ruthenium powder into a three-neck bottle, introducing chlorine gas to oxidize under alkaline condition, and oxidizing a product RuO4Absorbing by using a seven-grade hydrochloric acid absorption liquid to obtain a chlororuthenic acid solution;
（2）.NH4cl precipitation: placing the chlorine ruthenic acid solution obtained in the step (1) into a double-layer glass reaction kettle for stirring and heating, and adding superior pure NH under the stirring condition4Cl, cooling to room temperature and filtering to obtain (NH)4)2RuCl6Precipitating;
(3) high pressure hydrothermal reduction: reacting (NH) obtained in step (2)4)2RuCl6Adding ultrapure water into the precipitate, stirring and slurrying to obtain a suspension, putting the suspension into an autoclave with a polytetrafluoroethylene lining, and introducing hydrogen for reduction under the high-pressure hydrothermal reduction condition to obtain pure ruthenium and ruthenium oxide;
(4) thermal reduction in hydrogen: and (4) putting the ruthenium and the ruthenium oxide obtained in the step (3) into a tubular furnace, and introducing hydrogen for reduction to obtain a high-purity micron-grade ruthenium powder product.
The alkaline condition is that a saturated NaOH solution is added into a three-mouth bottle, the mass ratio of the coarse ruthenium powder to the NaOH is 1: 2-1: 5, and the ratio of the absorption liquid hydrochloric acid to the ultrapure water is 1: 1.
In step (1), the progress and end point of distillation were checked by using a cotton ball dipped in wet acidic thiourea in an absorption tube.
NH described in step (2)4The conditions for Cl precipitation were: the concentration of the chlororuthenic acid solution is controlled to be 10-50 g/L, and the temperature is controlled to be 50-100 ℃.
The high-pressure hydrothermal reduction conditions in the step (3) are as follows: the reduction temperature is 80-120 ℃, and the reduction time is 2-5 h.
And (4) carrying out hydrogen thermal reduction on ruthenium and ruthenium oxide at the drying temperature of 100 ℃, drying for 24 hours, wherein the reduction temperature is 500-900 ℃, and the reduction time is 1-5 hours.
The purity of the ruthenium powder prepared by the invention was measured by Glow Discharge Mass Spectrometry (GDMS), and the results are shown in Table 1.
Table 1 analysis results of ruthenium powder impurities.
Note: and (4) detecting by adopting GDMS analysis.
Example 2
The difference from example 1 is that the oxidative distillation: the mass ratio of the ruthenium powder to NaOH is 1:2, and the distillation temperature is 70 ℃. NH (NH)4Cl precipitation: the concentration of the chlororuthenic acid solution is controlled to be 30g/L and the temperature is controlled to be 80 ℃. The distillation time is prolonged, the concentration of the obtained chlorine ruthenic acid solution is low, and NH is generated4Precipitating with Cl to obtain fine precipitate particles, and finally obtaining ruthenium powder particles with the average particle size of 5 mu m;
example 3
The difference from example 1 is that NH is present4Cl precipitation: the concentration of the chlororuthenic acid solution is controlled to be 50g/L and the temperature is controlled to be 90 ℃. The high-pressure hydrothermal reduction conditions are as follows: the reduction temperature is 100 ℃, and the reduction time is 5 h. The dosage of ammonium chloride is reduced compared with that of the obtained (NH)4)2RuCl6The grain diameter of the grains is larger, the high-pressure thermal reduction time is prolonged, and the average grain diameter of the obtained ruthenium powder is 15 mu m;
example 4
The difference from the example 1 is that the hydrogen thermal reduction temperature is 900 ℃ and the reduction time is 3 h. The obtained ruthenium powder has white color, obvious metal luster and average grain diameter of 20 mu m.
Comparative example 1
The distillation mode is acid distillation, the distillation efficiency is low, the crude ruthenium powder can not be completely reacted, the NH4Cl precipitation temperature is insufficient, the ruthenium can not be completely precipitated, the color of mother liquor is darker, and the direct yield of the ruthenium is lower
Comparative example 2
In the process, when NH4Cl is precipitated, the concentration of the chlororuthenate is over 50g/L, the particle size of the formed (NH4)2RuCl6 particles is larger, the high-pressure hydrothermal reduction temperature and time are insufficient, the reaction is insufficient, and the (NH4)2RuCl6 is not completely reduced.
Comparative example 3
The hydrogen thermal reduction temperature is over 900 ℃, the reduction time is too long, and the obtained ruthenium powder is secondarily agglomerated.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. A preparation method of high-purity ruthenium powder is characterized by comprising the following steps:
(1) oxidative distillation: putting 99.9% of coarse ruthenium powder into a three-neck bottle, introducing chlorine gas to oxidize under alkaline condition, and oxidizing a product RuO4Absorbing by using a seven-grade hydrochloric acid absorption liquid to obtain a chlororuthenic acid solution;
（2）.NH4cl precipitation: placing the chlorine ruthenic acid solution obtained in the step (1) into a double-layer glass reaction kettle for stirring and heating, and adding superior pure NH under the stirring condition4Cl, cooling to room temperature and filtering to obtain (NH)4)2RuCl6Precipitating;
(3) high pressure hydrothermal reduction: reacting (NH) obtained in step (2)4)2RuCl6Adding ultrapure water into the precipitate, stirring and slurrying to obtain a suspension, putting the suspension into an autoclave with a polytetrafluoroethylene lining, and introducing hydrogen for reduction under the high-pressure hydrothermal reduction condition to obtain pure ruthenium and ruthenium oxide;
(4) thermal reduction in hydrogen: and (4) putting the ruthenium and the ruthenium oxide obtained in the step (3) into a tubular furnace, and introducing hydrogen for reduction to obtain a high-purity micron-grade ruthenium powder product.
2. The method for preparing high purity ruthenium powder according to claim 1 wherein: the alkaline condition is that a saturated NaOH solution is added into a three-mouth bottle, the mass ratio of the coarse ruthenium powder to the NaOH is 1: 2-1: 5, and the ratio of the absorption liquid hydrochloric acid to the ultrapure water is 1: 1.
3. The method for preparing high purity ruthenium powder according to claim 1 wherein: in step (1), the progress and end point of distillation were checked by using a cotton ball dipped in wet acidic thiourea in an absorption tube.
4. The method for preparing high purity ruthenium powder according to claim 1 wherein: NH described in step (2)4The conditions for Cl precipitation were: the concentration of the chlororuthenic acid solution is controlled to be 10-50 g/L, and the temperature is controlled to be 50-100 ℃.
5. The method for preparing high purity ruthenium powder according to claim 4 wherein: the high-pressure hydrothermal reduction conditions in the step (3) are as follows: the reduction temperature is 80-120 ℃, and the reduction time is 2-5 h.
6. The method for preparing high purity ruthenium powder according to claim 1 wherein: and (4) carrying out hydrogen thermal reduction on ruthenium and ruthenium oxide at the drying temperature of 100 ℃, drying for 24 hours, wherein the reduction temperature is 500-900 ℃, and the reduction time is 1-5 hours.
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